JPS62243660A - Coating compound and method for forming composite coating film - Google Patents

Abstract

PURPOSE:To form a coating film having chipping resistance and corrosion resistance, by applying a coating compound composition comprising a composition obtained by blending a specific olefin resin with an epoxy compound and a metallic oxide as a main component to either of a face to be coated or a layer between the coated face and a top coating film. CONSTITUTION:(A) An olefin resin which contains a chlorine group and a chlorosulfonyl group and has -10--60 deg.C static glass transition temperature is blended with (B) an epoxy compound containing two or more epoxy groups in one molecule and/or a metallic oxide to give a composition and a coating compound which comprises the composition as a main component and forms a coating film having 0--60 deg.C static glass transition temperature is applied to either of a face to be coated or a layer between the coated face and a top coating film.

Description

[Detailed Description of the Invention] This invention was originally developed to provide chipping resistance, especially for automobile body outer panels, etc.
The present invention relates to a coating composition useful for forming a multilayer coating film with excellent corrosion resistance and physical performance, and a method for forming a multilayer coating film with the above properties using the coating composition.

The painting process for automobile exterior panels usually consists of electrodeposition coating, intermediate coating, and top coating, but in recent years, the durability of the multilayer coating film for automobile exterior panels formed by this process has been improved. Problems are becoming more important, especially the problem of deterioration of the aesthetic appearance of the paint film due to impact peeling and the progress of corrosion of the steel plate of the vehicle body. for example,
Pebbles thrown up by the wheels of a car traveling on the road collide with the painted surface of the outer panel, and the impact causes the entire coating to peel off locally from the outer panel base material (steel plate). Peeling phenomenon, or so-called "chipping," often occurs. This phenomenon not only reduces the aesthetic appearance but also exposes the metal surface of the impact area on the outer surface of the car body, which quickly rusts and progresses to corrosion. Usually, chipping occurs. Peeling of the paint film is common on the bottom of the car body and leg area, but it also occurs on the hood and roof, and it is known that localized corrosion becomes quite noticeable after about six months to a year. In order to prevent the progression of corrosion of steel plates caused by this, various studies have been conducted on chemical conversion treatments on the surface of metal substrates, as well as electric tube paints, intermediate paints, and overcoat paints.For example, For chemical conversion treatment, iron phosphate coatings and zinc phosphate coatings with different crystal forms have been studied, but it is difficult to sufficiently improve the adhesion of the coating on the impact area.
Various studies have been conducted on the resins and/or pigments contained in intermediate and top coat paints, but so far no paint has been found that has sufficient adhesion to withstand chipping. Not yet reached.

Therefore, the present inventors solved the above-mentioned defects in a composite coating system consisting of, for example, electrodeposition coating - intermediate coating - top coating, etc., and improved the finished appearance, weather resistance, chemical resistance, etc., as well as chipping resistance and A coating composition useful for forming a multilayer coating film with improved physical performance and corrosion resistance, etc., and a method for forming a multilayer coating film with excellent corrosion resistance, etc. using the coating composition. As a result of conducting research on iron content, we were able to fully achieve the objective of Kowara and completed the present invention.

Therefore, according to the present invention, tl is: (1) A polyolefin resin containing a chlorine group and a talolsulfonyl group and having a static glass transition temperature of -10 to -60°C, containing two or more epoxy molecules in one molecule. The main component is an epoxy compound and/or a metal oxide, and the static glass transition temperature is O.
A coating composition characterized in that it is adjusted to form a coating at ~-60°C.

(2) An epoxy compound having two or more epoxy groups in one molecule and/or a metal in a polyolefin resin containing a chlorine group and a thalolsulfonyl group and having a static glass transition temperature of -10 to -60°C. The main component is a composition containing an oxide, and the static glass transition temperature is 0.
A method for forming a coating film, which comprises forming a coating film using a coating composition adjusted to form a coating film at a temperature of ~-60°C between the surface to be coated and the top coating film. is provided.

The present invention provides a coating composition (hereinafter referred to as "
The present invention discloses a method for forming a fc'6> layer coating film by improving these properties using the barrier coat (hereinafter referred to as "barrier coat" for short) and by using the barrier coat.

Regarding the barrier coat of the present invention, the polyolefin resin having both of the above functional groups and a specific static glass transition temperature can undergo a three-dimensional crosslinking reaction with the epoxy resin and (also) the metal oxide, and thereby form a The static glass transition temperature (hereinafter sometimes abbreviated as "TP point") of the formed coating film was adjusted to 0 to -60°C. ) has a higher elongation rate, better flexibility, viscoelasticity, and toughness than other coating films such as the above-mentioned heavy duty coatings, and also has good water resistance, corrosion resistance, chemical resistance, and adhesion. be. The multilayer coating film obtained by applying a top coat or the like to the barrier coat coating surface of the present invention, which has the specified composition and physical properties of the coating film formed in this way, has excellent interlayer adhesion and is resistant to chipping. The corrosion resistance, corrosion resistance, and physical performance were significantly improved.

The basic structure for improving the chipping resistance of the paint film formed according to the present invention is that an intermediate buffer layer made of the barrier coat film is provided in the multilayer paint film layer in order to absorb collision energy caused by pebbles, etc. It is in.

Specifically, a barrier coating film with 1 viscoelasticity, high elongation, and excellent flexibility (elasticity) and toughness was provided as an intermediate layer to absorb external impact energy. As a result, even if the multilayer coating film formed by the method of the present invention collides with the surface of the multilayer coating film, the impact energy is absorbed by the highly flexible barrier coat coating film provided below. As a result, the top coat film is exposed to impact φ
There are fewer cases of intrusion, less cracks and scratches, and there is no exposure of the base material of the coated object such as cracks. Furthermore, if the chi-nobbing resistance of the multi-layer coating film is improved in this way, problems such as corrosion and rusting of steel materials will naturally be solved, and in addition, the multi-layer coating film formed by the method of the present invention will be improved. The corrosion resistance itself is also significantly improved.

Furthermore, the multilayer coating film formed according to the present invention has excellent performance in terms of finished appearance, weather resistance, chemical resistance, impact resistance, and ease of removal.

The barrier foot and coating film forming method of the present invention will be explained in more detail below. Barrier coat: Polyolefin resin containing chlorine groups and chlorosulfonyl groups and having a static glass transition temperature of -10 to -60°C [( The main component is a composition obtained by blending an epoxy resin [(member component)] and (or) a metal oxide [component (C)] having an epoxy group of 2 # or more per molecule into the ω component], and , a coating composition that forms a coating film having a Tf point of 0 to -60°C.

First, component (a) is added to the polyolefin resin with chlorine groups (-
CL') and chlorosulfonyl group (-5O2Ct) are chemically bonded, and its static glass transition temperature is -
It refers to a resin that has a temperature of 10 to -60°C.

Examples of the polyolefin and in-resin having both functional groups include ethylene hydrocarbons represented by the general formula CnH21 (n is an integer of 2 to 10), specifically ethylene, propylene, pteci, and bene. Examples include polymers and copolymers consisting of #i2m or more selected from #te>, hebteshi, octe>, etc., and also include resins made by copolymerizing these ethylene hydrocarbons with vinyl acetate, etc. Among these, in the present invention, it is most preferable to use an ethylene homopolymer (ie, polyethylene), an ethylene-propylene copolymer, or the like.

17. Regarding the polyolefin resin containing the functional group, the number average molecular f#I/i is preferably 100,000 to 5,000,000, and the content of ethylene hydrocarbon in the copolymer with vinyl acetate etc. is 25% by weight. The above is suitable.

Further, in order to make the polyolefin resin contain all chlorine groups and chlorosulfonyl groups, it can be carried out by a method known per se, and the content is determined by the polyolefin resin io
o per part by weight, the chlorine group is 10 to 60 parts by weight, preferably 20 to 45 parts by weight, and the chlorosulfonyl group is 0.1 to 1 part by weight.
0 parts by weight, preferably 1 to 4 parts by weight.

Regarding these functional groups, the inclusion of chlorine groups inhibits the crystallinity of polyolefin resins, giving them flexibility, improving compatibility with other resins and solvents, and increasing surface energy. It has the effect of improving adhesion to the object to be coated and other $11 (lower, middle, and top coats) and improving the smoothness of the coated surface, and the content of chlorine is 1 part by weight. This kind of effect cannot be expected,
If the amount exceeds 60' parts, the coating film may become yellowed and water resistance may deteriorate. It is useful for forming a barrier coating film, and if the chlorosulfonyl group is less than 0.1 part by weight, a sufficient crosslinked structure will not be formed and the viscoelasticity will be insufficient, and if it is more than 10 parts by weight, the barrier coating will be There is a risk that the water resistance of the paint film will decrease.

The above component (a) used in the present invention is 1
2 points -10 to -60°C, particularly preferably -30 to -5
II)
If it is higher than -10℃, the chipping resistance of the barrier coating film will decrease, and if it is lower than -60℃ □, there is a risk that water resistance will decrease, so both are not preferable.
These 12 points can be easily adjusted by adjusting the chlorine group content of the polyolefin resin, and by adjusting the vinyl acetate content in the case of vinyl acetate copolymers.

Next, the (Tsuru component is an epoxy compound having two or more epoxy groups in one molecule, and can form a barrier coating film by crosslinking with the (ω component). Specifically, , bis(4-hydroxyphenyl), bis(4-hydroxyphenyl) 1.1-ethane, bis(4-hydroxyphenyl); bisphenols such as 4J-propane, phenol novolac, and cresol novolac. Aromatic epoxy resins obtained by the reaction of polyphenol compounds and epichlorohydrin, epoxy resins that form a J Nido layer by the reaction of hydrogenated bisphenols and epichlorohydrin, aliphatic jepoxy compounds, glycidylamine type epoxy resins, glyoxal type resins, etc. Examples include isocyanyl-type triglycidyl isocyanurate, among which bisphenols (including water bulk)
It is preferable to use a jepoxy resin, triglycidyl isocyanurate, etc., which are obtained by the reaction of ester and epichlorohydrin.

For these epoxy compounds, the epoxy equivalent weight is 10(l f /equivalent, especially 1000
It is preferable that it be within the range of r/prohibited.

Component (c) is a metal oxide, and is a compound useful as a crosslinking agent for component (a) or a crosslinking reaction promoter between component (a) and component (b). Examples of such metal oxides include magnesium oxide (M?), zinc oxide (ZnO), lead oxide (PbO), semiconductor zinc oxide (sintered Zn0), tungsten oxide (WO2), and tin oxide (SnO). □), and complexes consisting of these components, such as WO2-5n02
Among these, magnesium oxide (M
gO) and zinc oxide (ZnO) are preferably used.

The barrier coat used in the present invention includes the above component (a) and (
b) component or 2 consisting of component (a) and component (c)
The main component is a composition consisting of either a component yarn or a combination of component yarns consisting of component 1d (a), component (b), and component (c). Looking at the composition ratio of each of these components, (ω, (b) component or (a), (c
) In a two-component composition consisting of component (a) 100
In heavy urban areas, component (b) is 1 to 50 parts by weight, especially 2 to 50 parts by weight.
25 parts by weight, component (c) is 1 to 50 parts by weight, especially 3 to 3 parts by weight.
0 parts by weight is preferred. <a) In a three-component composition consisting of (bl and (C)), (a) component 10
Per 0 polymerization part, (b) component strength is 0.5 to 49.5 parts by weight, special VC is 1 to 24 parts by weight, and (c) component is 0.5 to 49.5 parts by weight.
5 parts by weight, especially 1 to 29 parts by weight, and (b)
The total amount of component Ii' and component (c) is preferably 1 to 50 parts by weight, particularly 2 to 30 parts by weight. In the above two-component system, (a).

(If component (b) is less than 1 part by weight, the crosslinking reaction of component (a) will not be sufficient, so water resistance, curling resistance, chemical resistance, etc. will tend to deteriorate, and if component (b) is less than 1 part by weight, If this happens, the weather resistance of the barrier coat film may decrease, and the interlayer compatibility with the top coat or intermediate coat on the barrier coat may decrease.In addition, in the (a) + (d) component system,
If component (c) is less than 1 part by weight, water resistance, gasoline resistance, chemical resistance, etc. may deteriorate.
If the amount exceeds 9 parts, the chipping resistance and impact resistance may deteriorate, the paint may tend to thicken, and it may gel during storage.

3 consisting of (a), (bl and (C) components)
In the component system, if the amount of component (C) is less than 0.5 parts by weight, curing properties may decrease, and if it exceeds 49.5 parts by weight, chipping resistance and storage stability may deteriorate. The barrier coat of the present invention also contains (b) in addition to the above (a) component.
It is preferable to use a composition formed by combining component (' or) (C) as the main component, or to apply the composition in a state in which these components are dissolved or dispersed in an organic solvent.

Examples of organic solvents include aromatic hydrocarbons such as becise, toluene, and xylene; aliphatic hydrocarbons such as hexane, hepta, octa, and deca; trichlorethylene, perchloroethylene, dichloroethylene, and dichloroethane. , cyclolbense.

In addition, organic solvents such as alcohols, esters, ketones, and ethers can also be used. In addition, the barrier coat according to the present invention may further contain color pigments (e.g., titanium white, carbon 7, etc.), extender pigments (e.g., asbestos, talc, clay, etc.), and rust-preventive pigments (e.g., , zinc powder, lead zinc oxide, lead chromate, zinc chromate, etc.), plasticizers (e.g., dioctyl 7-talate, tricresyl phosphate, dibutyl sepacate, etc.), anti-sagging agent 7i
'Il (911, ?, rr, aluminum stearate, silica gel, etc.) can also be blended in an appropriate amount that is normally used.

The barrier coat of the present invention needs to be adjusted so that 12 points of the coating film formed by the barrier coat are within the range of -0 to -60°C, particularly preferably -20 to -60°C. . If the T9 point is higher than 10°C, the chipping resistance will be lowered, and if it is lower than -60°C, the water resistance of the barrier coating film will be lowered, which are both undesirable.

Tf of barrier coat film, above (a), (b)
, which can be arbitrarily and easily adjusted depending on the composition and blending amount of component (c), but has good compatibility with component (a), such as rosin, petroleum resin (coumaron), ester gum,
The T1 point can also be adjusted using polybutadiene, epoxy-modified polybutadiene, polyoxytetramethylene glycol, etc., and the blending amount of these is preferably less than 10% of all components.

The barrier coat of the present invention also contains thiazoles (e.g., 2-mercaptobenzothiazole, 2-mercaptobenzothiazole, 2-mercaptobenzothiazole,
Pennthiazolyl disulfide, zinc salt of 2-mercaptobenzothiazole, N-cyclohexyl-2-pendithiazole nurphenamide, N-oxydiethyl〉-
2-be〉notiasolsulfenamide, Nt-butyl-'l-hensothiazolesulfenamide,
N. N-dicyclohexyl-2-benzothiazole 7ethyami F, 2(4-morpholinyldithio)benzothiazole, sodium salt of 2-mercaptobenzothiazole, etc.), thioureas (e.g., diethylthioflair, dibutylthioflair, (e.g., ethylene thiochloride, diracryl thiocrea, etc.), cyclams (e.g., tetramethyl thiclam disulfide, thioethyl thiclam disulfide, tetrabutyl thiclam disulfide,
dibencum methylene lenticlam tetrasulfide, tetramethylthiclam monosulfide, etc.), dithiocarbamates (e.g. zinc dimethyl dithiocarpame-1,
, dicycdiethyldithiocarbamate, zincylphenyldithiocarbamate, biperidinicum vesitamedylene dithiocarpamate, telluricum diethyldithiocarpamate, sodium dimethylthiocarbamate, sodium digtyldithiocarpa mate), guanidiodes (e.g.
Diphenyl guaniji, etc.)
Two or more types of Ff can be used. Contains a kneading accelerator! # is per 100 parts by weight of component (a),
5:I parts by weight or less, particularly 0.5 to 3 parts by weight, are suitable.

Among these, thiazoles and thioureas are preferred in the present invention, and ethylthiofrea is especially preferred.

Zero-Start 1 Barrier Coat requires that the T point of the coating film formed by the barrier coat be within the above range, and furthermore that the tensile strength elongation rate at break of the coating film must be within the above range. In a 0°C atmosphere, 100 to 1000%, preferably 300 to 800%, more preferably 4300 to 70%
It is desirable that it be at 0%.

In the present invention, the measurement of the T9 point of the component (a) and the barrier coat film is carried out using only the component (a) without containing other components such as a solvent, and the barrier coat film is 25μ based on the coating film forming the barrier foot
After painting and baking at 120℃ for 30 minutes,
The mercury amalgam method was used as a sasiple, and each was measured using a differential scanning calorimeter (Daini Seikokin DSC-
10 type). In addition, the elongation rate of tensile strength at break of the barrier coating film was determined using a universal tensile tester equipped with a constant temperature bath.
The values were measured at 0° C. using a Shimadzu Autograph Model S-D, the length of the sample was 20 cm, and the tensile speed was ij 2 0 wa 7 minutes.

Coating film forming method: The special feature of the multilayer coating film forming method of the present invention is that the barrier coating film of the present invention is formed on either of the surface of the object to be coated and the top coat layer. . That is,
Generally, a paint film is composed of a base coat layer, an intermediate coat layer, a top coat layer, etc. from the surface to be coated, making it a multilayer paint film (the base coat layer and intermediate coat layer are omitted). The special feature of the present invention is that it forms a barrier coating film layer between the layers. The coating material is mainly metal or plastic, but it can also be applied to glass, cement products, any inorganic product, wood, etc.Metals include, for example, iron, copper, aluminum, tin, zinc, and these. Alloys containing metals and plated or vapor-deposited products of these metals or alloys may be used, and it is preferable to pre-treat the surface with chromate, phosphate, etc. Examples of plastics include polyolefin resins such as polyethylene and polypropylene, ABS resins (a combination of acrylonitrile, butadiene, and styrene), nylon (polyamide resins), polycarbonate resins, acrylic resins, phenolic resins, and polyester resins. These objects may not only be made of a single material, but may also be made of dissimilar materials (for example, metal and plastic) combined and integrated. Specific examples of objects include vehicle bodies and parts for passenger cars, trucks, safari cars, autopilots, etc., electrical products, building materials, and structures.

In the present invention, main specific examples of coating film forming methods using rear coats on these coated objects include, but are not limited to, the following methods (processes).

(I): Object to be coated (metal) → Undercoat → Cold barrier coat → (Intermediate coat if necessary) → Top coat, (I): Object to be coated (metal) → Undercoat → Intermediate coat → Barrier coat Painting → Top coat, (I): Object to be coated (plastic) → Barrier coat coating stand (intermediate coating if necessary) → Top coating → Barrier coat coating stand (intermediate coating if necessary) → Ten coats Painting, In addition to the above, (V): Object to be coated (metal) → Barrier coat coating stand (base coat and/or intermediate coat if necessary) → Top coat, (Vl): Object to be coated (plastic) ) → Undercoat → Barrier coat → (Intermediate coat if necessary) → Top coat, (To): Material to be coated (plastic) → (Undercoat if necessary) → Intermediate coat → Barrier coat → Top coat, (Vl: Material to be coated (metal, plastic) → (undercoat if necessary) → Barrier coat → Intermediate coat →
It also includes a coating film forming method consisting of steps such as barrier coating → top coating.

Among the above methods (steps), (+) to (ff+) are particularly preferred.

Undercoat paint for metals and its coating method: As the undercoat paint, already known ones can be used, but for metal objects such as automobiles, cation type or undercoat type 1 can be used.
It is preferable to use an i-based paint.

First, Catio> type heavy duty paint is based on a resin with 7 basic amide groups, and is neutralized with acid.
This includes a cathode-deposited thermosetting electrodeposition coating material made water-soluble (water-dispersed), which is applied using the metal object as a cathode.

Examples of resins having 7 basic amino groups include (1) epoxy resins such as bisphenol-type epoxy resins, acrylic resins containing epoxy groups (or glycidyl groups), glycidyl ethers of alkylene glycols, epoxidized polybutadiene, and epoxidized products of novolak phenol resins; Addition of amine to epoxy group (oxirane ring) of group-containing resin;
■Unsaturated compounds with 7 basic amide groups (for example, N, N
Polymerization using glycols containing tertiary amino groups (e.g., N-methyljetanolamine)
Reaction with a polyisocyanate compound on a glycol component, where the glycol component is one component of the glycol E: ('4> Introduction of an amino group into the resin by the reaction of an acid anhydride and a diamine to form an iminoamine; etc.) Generally, resins in the range of about 20 to about 200 are suitable.

Examples of the amines used in the reaction (2) above include aliphatic, alicyclic, aromatic-aliphatic @primary amines, secondary amines, and tertiary amine salts. Onium salts can also be obtained by using secondary sulfide salts and tertiary phosphide salts.

Examples of neutralizing agents for neutralizing and water-solubilizing (water-dispersing) the resin or onium salt having 7 basic amide groups include acetic acid, hydroxyl acetic acid, propionic acid, acetic acid, lactic acid, Organic compounds such as glycine; sulfuric acid, hydrochloric acid,
Inorganic acids such as ricic acid can be used. The ratio fI/'i of the neutralizing agent to the above resin, the base number of the above resin (generally about 20
~ about 200) as a reference, about U, 1 of neutralization
A range of approximately 0.4 times the amount is appropriate.Also, as a crosslinking agent added to make the cationic electrodeposition coating heat-curable, a blocked polyisocyanate compound is generally used. and, thereby,
When the formed coating film is heated (usually at about 140°C or higher), the blocking agent dissociates, the incyanate group is regenerated, and active hydrogen-containing functionalities such as the aqueous dispersion groups present in the above-mentioned resins are activated. It cures by cross-linking with the group, and is also used in cationic heavy-duty paints, including pigments (residue additives, IR@ materials, anti-corrosion pigments, etc.) Pigment formulation!/':rResin solid content 100W
Usually 40 parts by weight or less, preferably more than 50 parts by weight, preferably from 50 to 150 TiL (by adding 50 parts by weight, it is possible to coat edges, bent parts, protrusions, etc. of the object to be coated with a thick film), Add a hydrophilic solvent, water, additives, etc. as necessary, dilute with de-iodized water etc. so that the solid content concentration is about 5 to about 401 J %, and adjust the pH to 5.5.
Adjust within the range of ~8.0. The cationic coating using the cationic electric eyebrow paint made in this way is usually carried out at a bath temperature of 15 to 35°C and a load voltage of 1 (70 to 400°C).
This can be done under the conditions of V using a metal coated object as a cathode. There are no particular restrictions on the thickness of the fluorite coating, but in general,
Based on the cured coating film, the range is preferably from lO to 40μ1,
In addition, the baking hardening temperature of the coating film is generally 100 to 2000℃.
range is suitable.

On the other hand, anionic heavy-duty paints are anodic deposition type electrodeposition paints that are mainly based on resins having carboxyl groups and are neutralized with basic compounds to make them water-soluble (moisture indoctrination). It is painted using the a& product to be coated as an anode.

Examples of resins with carboxyl groups include: Maleated resin obtained by adding maleic anhydride to drying oil (linseed oil, dehydrated castor oil, tung oil, etc.); @Polygetadiene (
1,2 type, 1.41p, etc.) Maleated polypure resin obtained by adding K maleic anhydride>; ■Resin obtained by adding maleic anhydride to unsaturated fatty acid ester of epoxy resin; ■High molecular weight polyhydric Alcohol (molecular weight approximately 10
00 or higher, including partial esters of epoxy resins and styrene/allyl alcohol copolymers)
polybasic acids (trimellitic anhydride, malicated fatty acids,
■ Carboxyl group-containing polyester resin (including those modified with fatty acids); ■ Carboxyl group-containing acrylic resin; ■ Polymerizable unsaturated monomer containing glycidyl group or hydroxyl group. Resins obtained by adding maleic anhydride to polymers or copolymers formed using products that warp with unsaturated fatty acids; In general, it is suitable for use in the range of about 30 to about 200, and can be used as a neutralizing agent to neutralize the carboxyl groups in these carboxyl group-containing resins and make the resins water-soluble (moisture indoctrination). teeth,
For example, monoethanolamine, jetanolamine,
Alkanolamines such as dimethylaminoethanol; alkylaminos such as diethylamine and triethylamine; and inorganic alkalis such as potassium hydroxide and sodium hydroxide can be used. The length of use of these neutralizing agents, the theoretical neutralization equivalent to the acid value of the resin, about (), 1 to about 1
．． 0 times fA- (preferably 0.4 to 0.8 times per movement 1 circle or appropriate).

Furthermore, as a crosslinking agent for making the above-mentioned resin thermosetting, low-molecular shield melamine resins such as hexakismethoxymethylmelamine, butoxylated methylmelamine, and ethoxylated methylmelamine can be used as needed. Furthermore, anionic electrolyte paints contain pigments (namely color pigments,
Anti-rust pigments, anti-rust pigments, etc. Pigment A1 can be applied in the same way as electric needle paint), a hydrophilic solvent, water, additives, etc. are mixed as necessary to reduce the solid content concentration to about 5.
~4011rP1% with deionized water etc. #l',! It can be prepared and served as an anion TLT appetizer by keeping the pH within the range of 7 to 9. The anionic coating can be carried out according to a conventional method, for example, under the conditions of a bath temperature of 15 to 35 DEG C. and a load voltage of 100 to 350 cm, using the object to be coated as an anode.

The thickness of the coating film is not particularly limited, but it is usually preferably in the range of lO to 40μ based on the cured coating film.

7 Nion 1'4T, wear eggr/'i 10 in principle
It can be cured by heating to a temperature in the range of 0 to 200°C, preferably 140 to 200°C, or it can be dried and cured at room temperature if an air-drying resin modified with an unsaturated fatty acid is used.

In the present invention, the undercoat paint for metal objects is not limited to the above electrodeposition paints, but includes, for example, acrylic resins, alkyd resins, polyester resins, basic polypropylene resins,
Organic solvent-based, water-based, or solvent-free undercoating that uses a mixture of polycrethane resin, melamine resin, incyanate resin, etc. as a vehicle component, and is room temperature drying type, heating drying type, or active energy ray radiation curing type. Paint can also be used,
These are coated by spray coating, dip coating, electrostatic coating, brush coating, etc., and the film thickness is not particularly limited, but is preferably 5 to 50 μm based on the dry coating film.

These undercoat paints can be applied directly to the metal surface to be coated, or can they be applied to the surface of a barrier coat that has already been applied to the surface of the object, as described in (V) above. In this case, the barrier coat may be applied either undried or partially dried.

Undercoating paint for plastics and coating method 2 Known undercoating paints can be used, such as polyester, phrethane-based, chlorinated polypropylene-based, and Holikrek-based paints, which can be applied to the glass by a conventional method.

Method of applying barrier coat: As is clear from the above-mentioned coating process, the barrier coat is applied to the undercoat film surface, intermediate paint film surface, plastic ivy (subject to be coated) or metal (subject to be coated) surface, etc. Particularly when the surface to be coated with one barrier coat is an undercoat or intermediate coat, the surface to be coated may be either uncured or t/'i cured. The coating method for the barrier coat is not particularly limited, and examples include spray coating, spreading, dipping, melt coating, and electrostatic coating. 20μ,
Particularly preferred is 5 to 10μ. Although this barrier coating film can be cured at room temperature, it is preferable to heat it to 50 to 180°C, especially 100 to 150°C. If the object to be coated is plastic, the heating temperature of the film is It is necessary that the temperature is lower than the heat distortion temperature of the plastic. Further, when applying a top coat or the like to the surface of the barrier coat, the barrier coat may be cured or uncured.

Intermediate coating and its coating method: As the intermediate coating, any known intermediate coating that has excellent layering properties, smoothness, sharpness, overbake resistance, weather resistance, etc. can be used. Specifically, examples include thermosetting intermediate coatings whose main vehicle components are short-oil or ultra-short-oil alkyd resins with an l\IJ length of 30% or less, or oil-free polyester resins and amine resins - these alkyd resins. and polyester resin has a hydroxyl value of 60 to 140
The amine resin preferably has an acid value of 5 to 200 and uses an unsaturated oil (or unsaturated fatty acid) as the paternal oil.
Needled melamine resin, urea resin, benzoguanamine resin, etc. are suitable. The blending ratio of both resins is 65-85% of alkyd resin and/or oil-free polyester resin based on solid lff weight.
, especially 70-80%, amine resin 35-15%, especially 3
It is preferably 0 to 20%. Furthermore, at least a portion of the above amine resin can be replaced with a polyisocyanate compound or a blocked polyisocyanate compound.

The form of the intermediate coating paint is most preferably an organic solution type, but it may also be a non-aqueous dispersion type using the above-mentioned vehicle components, a high sled type, a do type, an aqueous solution type, an aqueous (dispersion) liquid type, a powder type, etc. I don't mind. Furthermore, the intermediate coating requires extender pigments, coloring pigments, and other paint additives.
These intermediate coatings are paints that are applied to the surfaces of barrier coats, undercoats, plastics (objects to be coated), etc. It can be carried out in a similar manner, and the coating film thickness is preferably in the range of 10 to 50 μm based on the cured coating film, and the curing temperature of the coating film varies depending on the vehicle component. It is preferable to heat at a temperature in the range of 170°C, particularly 80 to 150°C, but if the object to be coated is plastic, the heating temperature is below the heat distortion temperature of the plastic member, generally about 60 to 150°C, particularly The temperature range is preferably from 80 to 120°C.

Top coat paint and its coating method: The top coat paint is a paint that is applied to the surface of a barrier coat film, intermediate coat film, undercoat film, etc., and is used to impart cosmetic properties to the coated object. Specifically, outside the finish W
We provide coatings with excellent properties such as t (sharpness, smoothness, gloss, etc.), weather resistance (gloss retention, color retention, chalking resistance, etc.), chemical resistance, water resistance, moisture resistance, hardening properties, etc. Paints known per se can be used, such as paints whose vehicle main component is an amino-acrylic resin, an amino-alkyd resin, an amino-polyester resin, or the like. The form of these paints is not particularly limited, and any form such as organic solution type, non-aqueous dispersion type, aqueous (dispersion) liquid type, powder type, and high solid type can be used. Drying or curing of the coating film is carried out by soft blasting at room temperature, heating drying, irradiation with active energy rays, or the like.

The top coat used in the present invention may be either an enamel paint containing a metallic pigment and/or a color pigment in a paint whose main component is the vehicle described above, or a clear paint containing no or almost no pigments. Examples of methods for forming a top coat film using these paints include the following methods: (1) Metallic paints prepared by blending metallic pigments and, if necessary, coloring pigments. A method of applying paint or a solid color paint containing color pigments and curing it by heating (metallic or solid color finish using the 1 coat 1 beta method).

(After applying 7I metallic paint or solid color paint and curing with heat, apply clear paint again.
, heat curing method again (metallic or solid color finish using 2-coat, 2-bake method).

■Paint with metallic paint or solid color brass,
Next, a clear paint is applied and then heated to cure both coats at the same time (metallic or solid color finish using a 2-coat, 1-bake method).

These top coat paints are preferably applied by spray painting, electrostatic painting, or the like. Nine, paint film! ! In the above (1), l is 25 to 4 (l tI
In the above ranges (1) and (3), the preferred weight range is 10 to 30 g for metallic paints and solid color paints, and the preferable range is 25 to 50 g for clear paints. The heat curing conditions can be arbitrarily selected depending on the +71 quality of the object to be coated, vehicle components, etc., but if the object to be coated is gold, generally 80~
Heating at 170°C, particularly 20-150°C, for 10-40 minutes is preferred. If the object to be coated is plastic, it may be below the heat deformation temperature of the plastic, for example 80 to
140°C is preferred.

Next, examples and comparative examples related to the present invention will be described.

■ Preparation of sample (1) Object to be coated (△): Steel plate (size 300 x 90 x 0.8 m+) chemically treated with Bonderite #3030 (manufactured by Nihon Parkerizing ■, zinc phosphate surface treatment agent).

In Table 1, the object to be coated (A-1) is a steel plate coated with a cationic Dengu paint, and the object (A-2) is anionic Dengu paint coated with an anionic Dengu paint.

(H: Polyamide resin plate after film coating with Ingropanol (
Size, 3(lOX'1)OXo, 8m).

(2 barrier coats): Polyethylene resin (number average molecular weight approximately 500,000) 10
Resin containing (chemically bonded) 25 parts by weight of chlorine groups and 3.5 parts by weight of chlorosulfonyl groups per 0.71 parts by weight (static glass transition temperature -35°C) 101) *'
Per part hydrogenated bisphenol type epoxy resin (
Manufactured by Toto Kasei@, Ke/Tote 5T-3000, Epoxy II235 f/T! #) 10 parts by weight and Accel 2
2-5 (Yoro Kagaku Kogyo@ Co., Ltd. commercial name, ethylene thiourea) 11X Ibe and an organic solvent (toluene)
Please be sure to mix it up.

(9): Magnesium oxide (MfO, manufactured by Kyowa Chemical Industry ■), per 100 parts by weight of the polyethylene resin containing chlorine groups and chlorosulfonyl groups used in (4) above,
Kiyowa Mag #30) 10 parts by weight and Accel 22-
The composition prepared by adding 51 parts by weight was mixed and dispersed in an organic solvent (toluene).

(0: per 100 parts by weight of the polyethylene resin containing chlorine and trigol sulfonyl groups used in (4) above, hydrogenated bisphenol type epoxy resin
Same as (A)) 10 parts by weight, magnesium oxide (same as (B) above)
Same as) 1 () parts by weight and accelerator 22-5 lv
The composition obtained by weight part was mixed and dispersed in an organic solvent (toluene).

(D) A composition consisting of CO2 is further added with titanium oxide (T
1 part by weight of 80wt.iOz) was added thereto, and the mixture was mixed and dispersed in an organic solvent (toluene).

(D: ethylene/propylene (4/6 weight ratio) copolymer resin (number average molecule [1,000,000]) 40 parts by weight of chlorine group and 1.5 parts by weight of chlorosulfonyl group per 100 parts by weight of copolymer resin (Static glass transition temperature -40℃) 10
A composition obtained by adding 20 parts by weight of epoxy resin (triglycidyl in cyanurate epoxy t9/02/tf) 5-layer acid zinc chloride and 22-51 parts by weight of Accel to 0Tii part, and an organic solvent (toluene) were mixed and dispersed.

(Fl: Polypropylene resin (number average molecular weight: 800,000) containing 10 parts by weight of chlorine groups (static glass transition temperature +10°C) was mixed with an organic solvent (toluene).

(3) Undercoat paint (A: Nireclone #9200 (manufactured by Kansai Paint ■, epoxy polyamide-based cationic electrodeposition paint, gray color).

(11: Nireclone +7200 (manufactured by Kansai Paint ■, polybutadiene-based anionic electrodeposition paint, gray color).

(4) Intermediate paint (A Near Mirak N-27-Lar (manufactured by Kansai Paint@)
aminopolyester resin intermediate coating).

(5) Topcoat paint (A Near Miracle White (manufactured by Kansai Paint ■, amino-alkyd resin topcoat paint, 1 coat 1 bake white imitation paint, pencil hardness I (20°C)).

Qj: Magikron Silver [manufactured by Kansai Paint■, amine acrylic resin thread topcoat pigment, 2-coat 1-bake silver metallic paint, pencil UiJ! degree H (20'C)
).

(C: Magikron Clear (manufactured by IA Nishi Paint Co., Ltd., aminoacrylic resin topcoat Ho+, 2-coat, 1-bake clear paint, pencil hardness H (20°C)).

■ Examples and comparative examples above! Using the prepared sample, the coating was applied according to the steps shown in Table 1 (() to form a multi-layer coating film.

1) Above the object to be coated! (1) The steel plate prepared in A was coated in advance with a heavy ring paint under the following conditions.

Cationic electrodeposition coating conditions: Bath solids concentration 19% by weight, Bath F
i1 degree 28℃, P) i6.5, load voltage approximately 250V, 1
8 (energized for + seconds).

Anion electrodeposition coating conditions: rPr solid content 'a degree 12wt 1%
, bath temperature 30℃, pH 7.8, load voltage approximately 200V,
Electricity applied for 180 seconds In both cases, after electrodeposition coating, wash with water and heat at 170℃ for 3 hours.
Bake for 0 minutes. The coating thickness is 20μ based on the cured coating. In Table 1, A-1 in the object column is a cationic electrodeposition coated steel plate, A-2 is an anionic electrodeposition coated steel plate, and B is a polyamide resin plate.

2) Barrier Coat Painting Painted with air spray so that the cured film thickness was 5 to 7 μm. In the column of baking conditions in Table 1, the C barrier coat film was baked at 120°C for 20 minutes, the ○ mark was left at room temperature for 10 minutes, and the intermediate coat and top coat P were tested without baking. : indicates.

3) Intermediate coating) was applied with air spray to a cured film thickness of 30 μm, and baked at 140° C. for 2 minutes. In Table 1, the intermediate coating is shown as
- indicates that it has been omitted.

4) Top coat In top coat painting, rlcIBJ uses a coating system in which top coat A is applied and baked at 140°C for 30 minutes.
The r2cIB color was made by applying clay paints B and C wet-on-wet and baking at 140℃ for 30 minutes.
Both? This is a system that simultaneously cures the film.

Coating V and film thickness are based on the hard coating film, topcoat A is 35μ, topcoat B is 15μ, and topcoat C is 30μ.
It is.

The T1 point and tensile strength elongation at break of the barrier coat I are as follows.

Performance Test Results In the above Examples and Comparative Examples, coating film properties were tested using a coated plate. The results are also listed in Table 1.

〔Test method〕

(*1) Chipping resistance: (1) Testing machine! f! :0-G-R Graperometer (Q
Panel company product) ■Stone to be sprayed: crushed stone with a diameter of approx. 15-20% ■Volume of stone to be sprayed 11: Approx. Attach the test piece to a test piece holding table at 20°C, and use air pressure to spray approximately 4 kg/al of crushed stone of approximately 5()〇 to the test piece, and then evaluate the coated surface condition and salt water spray resistance. The condition of the painted surface was visually observed and evaluated according to the following criteria, and the salt spray resistance was determined by subjecting the test piece to the water spray W test for 240 hours according to JTS Z2371, and then applying adhesive cellophane tape to the painted surface. Observe signs of rust, corrosion, and peeling of the paint from the exposed areas after rapid peeling ■ Paint surface condition (good): There are scratches due to the impact on some parts of the top coat. Only a slight amount of peeling was observed, and no peeling of the electrodeposition coating was observed at all.

Δ (slightly poor): Many scratches and peeling due to impact were observed in the top coat and intermediate coat, and peeling was observed here and there in the electrodeposition coat.

× (Poor): Most of the top coat and intermediate coat have peeled off, and the electrodeposited coating on the impact area including the impact area and its surroundings has peeled off - 0 ■Salt water spray resistance ◎: Rust, corrosion , One scratch on the paint film is nothing to be concerned about.

(T: #A1 corrosion and paint film peeling are slightly observed.

△: Ayu, corrosion and paint film)・Slightly more scuffing is observed.

×: Significant rust, corrosion, and paint peeling occurred.

(*2) Impact resistance: JTS K5400-1ri79 6.1:1
．． 3B rAccording to the upper right, a weight of 5002 is dropped from a height of 50 m in an atmosphere of -10°C to examine the model l'll@G): Completely different from the above: A few cracks and peeling occurred. After applying the tape and peeling it off, evaluate the painted surface.

(*4) Water resistance: One side is evaluated after soaking in water at 40° C. for 10 days.

rO): Q: No constant, Δ: Slight blistering, ×: Peeling (? & 5) Ganlin resistance: 30 minutes in commercially available Regieler Ganolin (20t: )
^1 After applying the penalty, evaluate the condition of the painted surface and adhesion.

◎：No abnormality △: Blistering and slight swelling occur. ×: Blistering and peeling occur

Claims (2)

[Claims] (1) An epoxy compound having two or more epoxy groups in one molecule and/or metal oxidation to a polyolefin resin containing a chlorine group and a chlorosulfonyl group and having a static glass transition temperature of -10 to -60°C. The product is a composition formed by adding a substance, and the static glass transition temperature is 0 to 6.
A coating composition that forms a coating film at 0°C. (2) An epoxy compound having two or more epoxy groups in one molecule and/or metal oxidation on a polyolefin resin containing a chlorine group and a chlorosulfonyl group and having a static glass transition temperature of -10 to -60°C. The main component is a composition formed by adding a substance, and the static glass transition temperature is 0 to -
A method for forming a multilayer coating film, which comprises forming a coating film formed from a coating composition that forms a coating film at 60° C. between the surface to be coated and the top coating film.